Fluoride-releasing composite materials

Abstract

The invention relates to fluoride-releasing, polymerizable dental compositeaterials having good mechanical stability, containing: (a) one or more ethylenically unsaturated polymerizable monomers based on di- or multi-functional (meth)acrylates; (b) initiators and optionally activators; and (c) usual fillers, and optionally pigments, thixotropic agents, plasticizers and other auxiliaries; and (d) one or more sufficiently water-soluble inorganic complex fluorides of the general formula A.sub.n MF.sub.m wherein, A is a monovalent cation, M is a metal of the III-V main group or II-V sub-group, n is a whole number from 1 to 3 and m is whole number from 3 to 6.

We claim: 
     
       1. A polymerizable dental material, comprising: (a) one or more ethylenically unsaturated polymerizable monomers selected from the group consisting of di- and multi-functional (meth)acrylates;   (b) initiators and optionally activators;   (c) usual fillers, and optionally pigments, thixotropic auxiliaries, plasticizers and other auxiliaries; and   (d) one or more sufficiently water-soluble inorganic complex fluorides of the following formula   A.sub.n MF.sub.m     wherein,     A is an alkali metal ion or NR 4   + , with R being C 1  -C 18  alkyl, phenyl or substituted phenyl,   M is a metal of the IIIA-VA group or IIB-VB group, with the proviso that M is not silicon or boron,   n is a whole number from 1 to 3, and   m is a whole number from 3 to 6.   
     
     
       2. The dental material according to claim 1, wherein R is a substituted phenyl and the substituents for phenyl are selected from the group consisting of C 1  -C 6  alkyl groups, C 1  -C 6  alkyl groups that are substituted by halides or nitrogen- or oxygen-containing groups, halides, C 1  -C 6  alkoxy groups and C 1  -C 6  alkyl amino groups. 
     
     
       3. The dental material according to claim 1, wherein R is a C 1  -C 6  alkyl group. 
     
     
       4. The dental material according to claim 1, wherein the group MF m  is TiF 6   2- , ZrF 6   2- , AlF 6   3- , ZnF 3   -  or PF 6 . 
     
     
       5. The dental material according to claim 1, containing: 10 to 55% by weight of component (a),   0.01 to 10% by weight of component (b),   40 to 85% by weight of component (c), and   2 to 25% by weight of component (d).   
     
     
       6. The dental material according to claim 1, containing: 14 to 44% by weight of component (a),   0.1 to 5% by weight of component (b),   50 to 80% by weight of component (c), and   5 to 15% by weight of component (d).   
     
     
       7. The dental material according to claim 1, containing: 14 to 44% by weight of component (a),   0.1 to 5% by weight of component (b),   50 to 80% by weight of component (c), and   5 to 10% by weight of component (d).   
     
     
       8. In a method of producing a fluoride-releasing dental material, the improvement which comprises: preparing a polymerizable composite that contains   (a) one or more ethylenically unsaturated polymerizable monomers selected from the group consisting of di- or multi-functional (meth)acrylates,   (b) initiators and optionally activators,   (c) usual fillers, and optionally pigments, thixotropic auxiliaries, plasticizers and other auxiliaries, and   (d) one or more sufficiently water-soluble inorganic complex fluorides of the following formula   A.sub.n MF.sub.m     wherein,     A is a monovalent cation,   M is a metal of the IIIA-VA group or IIB-VB group, with the proviso that m is not boron or silicon,   n is a whole number from 1 to 3, and   m is a whole number from 3 to 6.   
     
     
       9. The method of claim 8, wherein A is an alkali metal ion or NR 4   + , with R being C 1  -C 18  alkyl, phenyl or substituted phenyl. 
     
     
       10. The method of claim 9, wherein R is substituted phenyl and the substituents for phenyl are selected from the group consisting of C 1  -C 6  alkyl groups, C 1  -C 6  alkyl groups that are substituted by halides or nitrogen- or oxygen-containing groups, halides, C 1  -C 6  alkoxy groups and C 1  -C 6  alkyl amino groups. 
     
     
       11. The method of claim 9, wherein R is a C 1  -C 6  alkyl group. 
     
     
       12. The method of claim 8, wherein the group MF m  is TiF 6   2- , ZrF 6   2- , AlF 6   3- , ZnF 3  or PF 6   - . 
     
     
       13. The method of claim 8, wherein the dental material is selected from the group consisting of a permanent dental-filling material, a temporary dental-filling material, a dental crown, a provisional dental crown, a dental bridge, a provisional dental bridge and a dental cement. 
     
     
       14. A method of producing a fluoride-releasing composite, which comprises: (i) preparing a polymerizable composite that contains (a) one or more ethylenically unsaturated polymerizable monomers selected from the group consisting of di- or multi-functional (meth)acrylates,   (b) initiators and optionally activators,   (c) usual fillers, and optionally pigments, thixotropic auxiliaries, plasticizers and other auxiliaries, and   (d) one or more sufficiently water-soluble inorganic complex fluorides of the following formula   A.sub.n MF.sub.m     wherein,       A is a monovalent cation, M is a metal of the IIIA-VA group or IIB-VB group, with the proviso that m is not boron or silicon,   n is a whole number from 1 to 3, and   m is a whole number from 3 to 6; and   (ii) polymerizing said polymerizable composite.   
     
     
       15. The method of claim 14, wherein A is an alkali metal ion or NR 4   + , with R being C 1  -C 18  alkyl, phenyl or substituted phenyl. 
     
     
       16. The method of claim 15, wherein R is a substituted phenyl and the substituents for phenyl are selected from the group consisting of C 1  -C 6  alkyl groups, C 1  -C 6  alkyl groups that are substituted by halides or nitrogen- or oxygen-containing groups, halides, C 1  -C 6  alkoxy groups and C 1  -C 6  alkyl amino groups. 
     
     
       17. The method of claim 15, wherein R is a C 1  -C 6  alkyl group. 
     
     
       18. The method of claim 14, wherein the group MF m  is TiF 6   2- , ZrF 6   2- , AlF 6   3- , ZnF 3   -  or PF 6   - . 
     
     
       19. The method of claim 14, wherein the dental material is selected from the group consisting of a permanent dental-filling material, a temporary dental-filling material, a dental crown, a provisional dental crown, a dental bridge, a provisional dental bridge and a dental cement. 
     
     
       20. A polymerizable dental material, comprising: (a) one or more ethylenically unsaturated polymerizable monomers selected from the group consisting of di- or multi-functional (meth)acrylates;   (b) initiators and optionally activators;   (c) usual fillers, and optionally pigments, thixotropic auxiliaries, plasticizers and other auxiliaries; and   (d) one or more sufficiently water-soluble inorganic complex fluorides of the following formula   A.sub.n MF.sub.m     wherein,     A is a monovalent cation,   M is a metal of the IIIA-VA group or IIB-VB group, with the proviso that M is not boron,   n is a whole number from 1 to 3, and   m is a whole number from 3 to 6.   
     
     
       21. The dental material according to claim 20, wherein the group MF m  is SiF 6   -2 . 
     
     
       22. In a method of producing a fluoride-releasing dental material, the improvement which comprises: preparing a polymerizable composite that contains   (a) one or more ethylenically unsaturated polymerizable monomers selected from the group consisting of di- or multi-functional (meth)acrylates,   (b) initiators and optionally activators,   (c) usual fillers, and optionally pigments, thixotropic auxiliaries, plasticizers and other auxiliaries, and   (d) one or more sufficiently water-soluble inorganic complex fluorides of the following formula   A.sub.n MF.sub.m     wherein,     A is a monovalent cation,   M is a metal of the IIIA-VA group or IIB-VB group, with the proviso that m is not boron,   n is a whole number from 1 to 3, and   m is a whole number from 3 to 6.   
     
     
       23. The method of claim 22, wherein the MF m  group is SiF 6   2- . 
     
     
       24. A method of producing a fluoride-releasing composite, which comprises: (i) preparing a polymerizable composite that contains (a) one or more ethylenically unsaturated polymerizable monomers selected from the group consisting of di- or multi-functional (meth)acrylates,   (b) initiators and optionally activators,   (c) usual fillers, and optionally pigments, thixotropic auxiliaries, plasticizers and other auxiliaries, and   (d) one or more sufficiently water-soluble inorganic complex fluorides of the following formula   A.sub.n MF.sub.m     wherein,       A is a monovalent cation, M is a metal of the IIIA-VA group or IIB-VB group, with the proviso that m is not boron or silicon,   n is a whole number from 1 to 3, and   m is a whole number from 3 to 6; and   (ii) polymerizing said polymerizable composite.   
     
     
       25. The method of claim 24, wherein the MF m  group is SiF 6   2- .